Patent GB-762811-A (GB)
Title: Improvements in the production of gasoline from oils by catalytic pressure hydrogenation
IPC: C10G47/12
Filed: 1954-08-05
Abstract: Heavy oils, e.g. destructive hydrogenation residues, shale and tar oils, are converted into gasoline of high octane value by passing the oils under pressures from 50 to 600 atmos, and at 250-450 DEG C. in admixture with 0.5-4 cubic metres hydrogen per kilogram oil over synthetic silicates of metals of the 5th-8th Groups of the Periodic Table and passing the products formed to a second stage, with further addition of hydrogen if required, at 360-550 DEG C. and at pressures above 50 atmospheres over an aluminium or magnesium silicate carrier containing an oxide or sulphide of one or more metals of the 6th to 8th Groups.  The silicates used in the first stage may contain up to 10 per cent of a compound of aluminium or magnesium; oxides or sulphides of molybdenum, tungsten, nickel or cobalt, cobalt molybdate, or nickel tungstate may be applied.  The second stage catalyst may also contain copper, silver, zinc, lead, thorium, titanium, zirconium, tin or vanadium.  The heavy oils are preferably pretreated in a reaction chamber filled with rings or porous inert materials heated to 300-500 DEG C.  In examples (1) A middle oil having an initial b.p. of 220 DEG C. and 90 per cent of which boils up to 350 DEG C. is passed with 2.5 cubic metres of hydrogen per kg. oil under a pressure of 260 atmospheres and at 405 DEG C. and with a throughput of 0.9 kg. oil per litre catalyst over nickel silicate containing 10 per cent molybdic acid.  The product in the vapor phase is passed with 2 cubic metres hydrogen per kg. oil and with a throughput of 1.5 kgs oil per litre catalyst per hour at 368 DEG C. and 260 atmos. over a catalyst comprising synthetic aluminium silicate containing 3.5 per cent molybdic acid.  A 60 per cent conversion to gasoline containing 25 per cent aromatics is obtained. (2) A middle oil obtained by the carbonisation of Spanish shale and containing 1.8 per cent phenols is passed with hydrogen at 240 atmospheres and 390 DEG C. over a catalyst comprising cobalt silicate containing 5 per cent Al2O3 impregnated with 10 per cent molybdic acid.  The product which is free from phenols is passed at 420 DEG C. and 240 atmos. over a synthetic aluminium silicate containing 3.5 per cent MoO3; a 65 per cent conversion to gasoline is obtained (3) The middle oil of Ex. 1 is passed with 1.8 c.m. hydrogen per kilogram oil and with a throughput of 0.5 kg. oil per litre catalyst per hour at a temperature of 380 DEG C. and under 75 atmos. pressure over a catalyst comprising nickel silicate containing 10 per cent MoO3. The temperature is gradually raised to 440 DEG C. to compensate for loss of activity of catalyst which is regenerated after a period of 4 months.  The product from the first stage is freed from nitrogen and passed with added hydrogen over the aluminium silicate-molybdenum oxide catalyst used in Ex. 2 at an initial temperature of 350 DEG C. raised gradually to 500 DEG C. 48 per cent conversion to gasoline having an octane number of 83 is obtained.  The catalysts used in the above examples are prepared as follows (1) (a) nickel carbonate dissolved in dilute H2SO4 is mixed with waterglass solution.  The clear sol is precipitated at pH 9-10 with 10 per cent soda solution. The washed precepitate is dried at 80-100 DEG C., shaped, heated to above 400 DEG C. and impregnated with ammonium molybdate to give 10 per cent MoO3 on the finished catalyst and finally heated to 400 DEG C. (b) a solution containing aluminium nitrate, ferric chloride, magnesium nitrate, and hydrochloric acid is added with stirring to waterglass solution.  After mixing, the solution is neutralzed wth ammonia and the deposited silicate which is obtained as a precipitate is washed, dried, shaped, impregnated with ammonium molybdate and dried at 500 DEG C. to give a content of 3.5 per cent MoO3.  (2) (a) cobalt carbonate dissolved in concentrated HCl is mixed with water-glass solution and cobalt silicate is precipitated by addition of soda solution.  After washing, the precipitate is mixed with freshly precipitated Al2O3 the paste homogenized, kneaded and dried to give pills containing 5 per cent Al2O3 which are impregnated with ammonium molybdate solution dried and heated to give pills containing 10 per cent MoO3 (b) aluminium sulphate is dissolved in water containing H2SO4, mixed with sodium silicate solution in a turbo mixer and the silicate is precipitated by addition of ammonia; the washed precipitate is mixed with ammonium molybdate, dried, shaped into pills, and heated.